Acylamino-anthraquinone vat dyestuffs



' r l'k tq for example, from- 1 aminoanthraquinonyl-Z-aryl ketones orfrom 1 :i-dihalogen-anthraquinonyl- Patented Sept. 11, 1951 ACYLAMIN -ANTHRAQUINON E VAT DYESTUFFS Eduard Moergeli, Neuewelt, Munchenstein,Switzerland, assignor to Ciba Limited, Basel, Switzerland No Drawing.Application February 2, 1949, Serial No. 74,264. In Switzerland January30, 1948 12 Claims. (Cl. 260-377) 1 According to this invention valuableanthraqiiinone vat dyestuffs are made by introducing into a1-aminoanthraquinonyl-Z-aryl ketone in the 4-position of theanthraquinone nucleus an amino group which is acylated by an aromatic,or aliphatic-aromatic carboxylic acid.

As starting materials for the present process there may be'used, forexample, l-aminoanthraquinonyl-2-aryl ketone'. The latter may beobtained in known manner, for example, by reactmg chloride with anaromatic compound in the presence of aluminium chloride to form thecorresponding ketone. As aromatic compounds there may be employed, forexample, unsubstituted acting the resulting halogen derivative-with acarboxylic acid amide appropriate for the pres-Lamino-anthraquinone-Z-carboxylic acid aromatic hydrocarbons containing6-12 carbon atoms, such as naphthalene, .diphenyl and especiallybenzene, and also substituted aromatic hydrocarbons which are capable oftaking part in the aforesaid reaction, such as toluene,halogen-benzenes, etc. I

Y'The'se'startin'g materials are converted, in accord'ance with. thepresent invention, into 1- amino-i-acylamino anthraquinonyl-2-arylketones of the general formula (1]) NET- O O-R at most 13 carbon atoms,which may contain -'substituents' in the aromatic nucleus.

Advantageously, these compoundsare made by mouoa'cylating a l:4-diaminoanthraquinonyl-2- The latter ketones are obtainable,

2-aryl ketones by the process of U. S. patent application Ser. No.74,265, filed February 2, 1949.

, It is also possible in known manner to exchange .Ia'halogen atomdirectly for an acylated amino group. Thus; the new, dyestuii's can bemade, for example, byv introducing a halogen atom into ai-aminoanthraquinonyl2-aryl ketone in the 4- :;position of theanthraquinone nucleus, and reent invention. 4

Illustrative of the residue CO-R2 in the above formula are the residuesof carboxylic acids of the aromatic or aliphatic-aromatic series, whichcontain at most 13 carbon atoms. There may be mentioned, for example,the residues of benzoic acid and of nuclear substitution products ofbenzoic acid, such as para-chloro-, parabromoor 2:4- or 2;5-dichloro.-ben zoic acid, para-toluic acid, para-methoxyjor'para-ethoxybenzoicacid, and also fl-naphthoic acid, diphenyl carboxylic acid, cinnamicacid, etc, c

The products so obtained are valuable vat dyestuffs. They aresuitableior dyeing and especially for printing a very wide variety ofvegetable fibers such as cottonflinen; and "artificial silk and staplefibers ofregeneratedcellulose: .In general the yield bright violet to.reddish blue tints.

It is surprising that valuable dyestuffs yielding deep tints can beobtained in this manner. It could not be expected that violettoblue-dyeing vat dyestufl's of good absorptive capacity would be obtainedby introducing a'simple aryl ketone radical into the Z-position oflamino-i-benzoylamino-anthraquinone which is not suitable for dyeing. InGerman Patents Nos. 545,001 and 546,229 are disclosed red-dyeing vatdyestufi's which contain two molecules of l-aminoanthraquinone linkedtogether in their 2-positions' by a 4:4-diketo-diphenyl bridge. It isstated that 1-amino-2-diphenoyl-anthraquinone, which contains only oneamino anthraquinone molecule, possesses no dyeingpr'operties, as theleuco compound has no affinity for cellulose fibers.In-contradistinction to this known'producthavingno dyeing properties,the new products of the present invention, which contain an acylaminogroup in the 4-position of the anthraquinone nucleus, have verypronounced dyeing properties. The fact that'the tints of the dyeings aremarkedly shifted towards blue is of-importance, having regard to therelative simplicity of the molecule.

The dyeings and prints produced with the new dyestuffs are in generaldistinguished-by excellent fastness to light and chlorine. Specialmention must also be made of the fastness to rain drops of these dyeingsand prints. The new dyestufls are also of special interestowin'g to the.fact that they discharge well and therefore provide very fast grounddyeings for goods subjected to color discharge.

The following examples illustrate an advantageous method of" making thenew products in accordance with the invention, wherein an acid chlorideis reacted with a 1:4-diaminoanthraquinonyl-2-aryl ketone in thepresence of an acid-binding agent under conditions such that nodi-acyllatedi prodiietse are formed".- It iSf surprising'tliat' realdifficulties in this respect are not encountered, especially if undulyhigh reaction temperatures and a great excess of the acid-' chloride areavoided. In the examples-therpzrrts are'by weight unless otherwisestated, and: the

relationship of parts by weight to parts by volume is the same as thatoff the kilogram" tdthe literz.

Example 1 A mixture of 6.6 parts of lz-4i -diaminoez-(parae- 3:9 partsof. para-chlorobenzoyl chloride, 6 parts chlorobenzoyl) -anthraquinone,4.5 parts of para- 7 is: separated by filtering with: suction whilestill warm; and it" is. freed-1 from adherent solvent by washing; with:alcohol and. wa-tera. It-.- dissolves in concentrated sulfuric acid witha green coloraticngtdyes cotton and! viscose: artificiaL silk: from anolive-green vat reddishebl-ue. tintshaving good properties; of: wetfastness, and. yields on cotton prints ofpowerfulzreddish blue tints vhaving ex.- cellent fastnesstoilightl using: in this example-instead:of: the: paraciiloiioberizoylv chloride, 535 a parts of para-bromoebenzoyb chloride, and proceeding; otherwise. in

can. be used; for printing: cotton; and also -for producing: whitedischarges. By acy-la'tion with am. equivalent: quantity of: para-toluicacidchloride. at dyestuft is: obtained: which; yields. prints cottonoff." somewhat bluer: tints= Dyestuffs which: are" obtained. withani'soyl. chloride-- or 2:5-dich1brobenzoyl" chloride" in 150 parts byvolume of" ortho-dichibrobnzene and 6 parts by volume of pyridine for 45minutes at 110 -115 C. Thewhcle is allowedto cool somewhat and that samemanner: there isobtained. a dyestufi very sim'ilazrtinotorial.properties, which is separated by filtering with suction. It dissolvesin concentrated sulfuric acid with Y a. Bordeaux red coloration. Ityields on cotton prints of violet tints which are fast to light andraindrops; I

The 1 4 diamino z-(para-chlorobenzoyl) anthraquinone used in theforegoing examples melts at 227 C. (uncorrected) and is obtainedaminatiomof 1 :4-dichloro-2- (para-chloro- P beuzoyD-anthraquinone(melting at 245 C.

uncorrected) Example 3 A mixture of: 6 parts of 1:4 -diamino -2-(metazpara dichlorobenzoyl) anthraquinone,

by volume of 'pyridine and 150 parts by volume of:ortho1-dichlorobenzeneis stirred for 1 hour at 110 C. The whole; is then allowed to coolsomewhatand thedyestuff which crystallizes in bluer-ieedles-v isseparated byfiltering withsuction. It dissolves in. concentratedsulfuric acid with a green coloration: and yields on cottonpure reddishblue prints having good properties of fastness, especiallyanexcellentfastness tolig ht.

Byusing thisexample, instead of theparachlorobenzoy-l chloride, anequivalent, quantity of: benzoyl chloride: there is obtained. a dyestuiiof the formula" a which yields. somewhat less reddish blue tints on" thefibre. I

The 1 :4-diamino 2 (meta :parat-dichiorohenzoyl) -anthraquinone used-inthis example is obtained from 1 :4-dichIoro-2- (meta para-dichlorcbenzoyl) -anthra'quinone" (melting at 213-213;? C;

uncorrected), by the toluene sulfonamide method.

It crystallizes from ortho-dichlorobenzene in the form of blue needlesand melts at 243 C. (uncorrected) Example 1.7 parts of para-toluic'acid" chloride are added dropwise to a suspension of 3 parts of1:4-diamino-2- (metazpara dichlorobenzoyl) -anthraquinone. in. QO partsbyv volume of. orthor-dichloro benzene. and 3v parts by volume ofpyridine, and the whole is then heated for 1 hour at 1104-1553 C. Aftercooling. to -80 C. the. dyestufl which crystallizes in the form. of blueneedles is. sepmated by filtering. It dissolves-in concentratedsulfuric-acid witha green coloration and in the vat with an. olive-greencoloration,v and yields on cotton prints havingv clear reddish-bluetints which are of excellent fastness: to chlorine and light.

By using in this-example instead of. the aforesaid acid chloride, anequivalent quantityotparafiuorobenzoyl. chloride, there; is. obtained a.dyestuff. which. yields on cotton and viscose artificia silk somewhatmore reddish blue prints.

Example 5 A. mixture of 6' parts of 1:4'-diami'no-2- (meta:para-dichlorobenzoyl) -anthraquinone, 4.5

parts of 2:5-dichlorobenzoyl chloride, 6 parts by volume of pyridine and150 parts by volume of ortho-dichlorobenzene is stirred for 1 hour atCL, and then filtered at 90 C. In this rna'nneithe're is obtained adyestufl' which yields irection and viscose artificial silk printshaving violettint'swhich are fast to raindrops and light.

chlorobenzene is stirred for 1 hour at 110-115" 0.

After working up, the resulting 1-amino-4- (parachlorobenzoylamino) 2(para-fluorobenzoyllanthraquinone of the formula is obtained in the formof a blue dyestufl; 'It dissolves in concentrated sulfuric acid with agreen coloration and yields prints having reddish blue tints.

.By acrylation with another acid chloride, such as para-bromobenzoylchloride, para-iodo-benzoyl chloride or meta-d:-triiluoromethylbenzoylchloride, there is obtained a dyestufi having similar tinctorialproperties. On the other hand the dyestufi obtained by acylation withs-naphthoic acid chloride yields substantially bluer tints.

Example 7 41 parts of 1:4-diamino 2 benzoylanthraquinone are heated in23 parts of para-chlorobenzoyl chloride, 600 parts by volume oforthodichlorobenzene and parts by volume of pyridine for 4 hours at115-125" C. After cooling, the dyestufl of the formula NH-O 0001 isseparated by filtration, washed with alcohol and then with water, anddried. It dissolves in concentrated sulfuric acid with an olive-greencoloration and dyes fibers from a hydrosulfite vat, after beingsuspended in air, reddish-blue tints of excellent fa stness to light.

By acylation with para-bromobenzoyl chloride or benzoyl chloride thereare obtained dyestuffs .which yield somewhat bluer tints as comparedwith the dyestufi obtained in the preceding paragraph of this example.

Example 8 of para-toluic acid chloride there is obtained,

6 a dyestuflf which yields onagtextile materials prints of somewhatbluer tints.

Example 9 3 parts of 1:4-diamino-2#n-aphthoyl-anthraquinone arecondensed with 2 parts of parachlorobenzoyl chloride in 60 parts byvolume of chlorobenzene and 3 parts by volume of pyridine by stirring atC. for =34; hour, whereby naphthyl [1 amino 4 (para-chlorobenzoylamino)anthraquinonyl 21- ketoiie' is formed.

The dyes'tuifof the formula which precipitates in the form of. needleshaving a bronze lustre yields on cotton prints of approximately the sametint as those of the product obtained in Examples by acylating withnaphthoic acid chloride.

The 1:4 diamino-2-naphthoyl-aminoanthra-- quinone-used as startingmaterial is a, blue crystalline powder melting at 209 C. (uncorrected).It is obtained from naphthyl-(lz'4-dichloranthraquinonyl-2)-ketone bythe toluene sulphonamide method. The latter compound can be obtainedfrom l:4-dichloranthraquinoneFZ-car- .boxylic acid chloride andnaphthalene by the Friedel and Crafts synthesis. It crystallises fromtoluene in the form of yellowish lamellae and then melts at I'll-173 C.(uncorrected). By analysis to determine thechlorine, carbon and hydrogencontents of the ,product it is found to correspond closely to the.empirical formula C25H12O3Clz. Which of the two possible compounds inview of the nuclear isomerism is present, or whether the product is amixture of the two forms difficult to" separate; has not beendetermined. 1

Example 10 a 2 parts of para-chlorobenzoyl. chloride and 2.8 parts of 1;4}diamino 2 anis'oyl-anthraquin one are reacted together in GOparts byvolume of chlorobenz'ene and 2.8 parts bylyolume of pyridine by beingheated for /2 hour at 110- C. A dyestufi' is obtained which yields oncotton prints having powerful reddish-blue tints. The prints also havean excellent fastness to light.

Example 11 2 parts of 1-amino-4-para-chlorobenzoy1-amino-2-benzoylanthraquinone obtained as described in the-firstparagraph of Example 7 are .vattedwith ,8 parts by volume of causticsoda .ume ofcaustic soda solution of. 36 B. -and 2 parts of sodiumhydrosulflte. 100 partsof :well wetted cotton are entered at 25 C., 50parts of sodium chloride are added after V4 hour, and dyeing iscarriedonat 25-30" C. for 1 hour. The cotton is squeezed andcentrifuged, oxidized in the air, rinsed cold, acidified, again rinsedand, if desired, soaped at the boil. The material is dyed a fastreddishblue-tint,

1. An anthraquinonewat:dyestufii f thflzfi eral formula wherein R1stands-101' an aromatic-radical eon taming. from 6 to 12 carbon atomsand is free from ionizable salt-forming substituents, and -CO-R: standsfor theiradlca'l or an aromatic monocarboxylic acidiot "the formula;HO-SO Rz containing 'atimost- 13 carbon atoms.

I 3.1m anthraquinone'vat dyestufl" of the general formulawhereinxRrstandsrfors an: aromatic radical contaming from 6 to 12 carbon atomsandiis tree from ionizable salt-10mins; substituents, and .CO-Ra standsfor theradical of a benzene monocarboxylic. acid or; the. .fcrmulaHO-CO-Rz containing. at-most' 9' carbon atoms.

. 4. anthraquinone, vat". dyestufl 01 the general formula v n NHCO.R;1'wliereln'R'r stands fora benzene radical substituted at most by; twohalogen atoms, anfi --GO -R: stands for the radical of a monoeanbOylio-aoid of the formula HO-SORa-con- .,;mm; at most 13 carbon atoms andbelonging to" one of the series: mmam aromatic;

An anthraaquincne vat dyestuflfofthe' general iormul'a I Z 8 wherein;Br: stands for a -benzeue redial; nub stituted at most by two halogen.atoms. and -CO'-Ra :stands for-the. radical or anaromatic monocarboxylicacid of the formula HO-CO-Ra' containing at most 13 carbon atoms.

'6. 11m: anthraquinone vat dyestufi o1; tbesenoral: formula wherein R1stands for a. benzene'fradical substituted at most by two halogen atoms,and -CO-Rz stands for the radicaloi a benzene monocarboxylic-aoid of theformula H0COR: containing at most 9 carbon atoms.

7. An anthraquinone vat dyestufl of the gem eraliormula j v V QNHI QO-Riwherein R1 and R2 stand for benzene-tedious containing together atleasttwo halogen atoms but being free from, other substituents. 8. vat,Qyestuflfof theformula 11. The vat dyestufi of'the formula 12. The vatdyestufl of the formula REFERENCES CITED 0 NH, The following referencesare of record in the file of this patent: 0000011. 5 UNITED STATESPATENTS Number Name Date 2,299,141 Hauser Oct. 20, 1942 NHO 0001 OTHERREFERENCES 19 Barnett: Anthracene and Anthraquinone EDUARD MOERGELI. 1

1. AN ANTHRAQUINONE VAT DYESTUFF OF THE GENERAL FORMULA